Chlorinated hydrocarbon resin



Patented Nov. 4, 1941 cnLoamarEn maocaanon an sm Richard -Waller,Helsingfors, and Charley Gustaisson, Imatra, Finland,

Bjorkstei, Chicago, Ill;

No Drawing. Application November'l, 940,

Serial N0. 364,752

11 Claims.

This invention relates to compositions of matter and to methods ofpreparing such compositions, and more particularly to varnishes,lacquers and resinsprepared from inexpensive hy' drocarbon products.

This application is a continuation in part of our copending application,Serial No. 213,185, flied June 11, 1938."

Heretofore, resins have been prepared from hydrocarbons by variousprocesses. However, the

assignors to Johan (c1. zen-z) with a polymerization catalyst of theFriedel- Craft type,preferably aluminumchloride, with out' the additionof non-chlorinated or partially chlorinated hydrocarbon mixturescomprising essentially a substantial amount of atleast one member of theclass consisting of unsaturated prior methods which have employed as rawmaterials inexpensive products containing mixtures, of a great number ofdiflerent hydrocarbons, have produced as by-products heavy resinousoils, or very low .melting point solid materials,

which, unless removed, h'ave imparted undesirable properties in theresulting products; for

example, excessive softness, tackiness, and the like. The removal ofthese undesirable by-products has been attained only by inconvenient andcostly steps in the processes of manufacture, such as, for example,separation of these by-produ'cts from the resins'by steps involvingextraction,

distillation, or the like.

One of the objects of this invention is to pro-' vide a method ofpreparing a varnish-like dry-' ingsolution of hydrocarbon resins frominexpensive, heterogeneous hydrocarbon materials, which solutionswhenexposed to the atmosphere or air dry to form hard tenacious films ofgood adhesion to glass, metals, and the like surfaces.

The process of manufacture of the solutions does not involve the step ofseparatingor removing any heavy oil, or soft res in fraction from the-reaction product.

Another object of this invention is to provide a method of preparing,from inexpensive hydro 1 cyclic hydrocarbons andof na'phthenes prior tothe polymerization step.

On completion of the polymerization reaction the catalyst is preferablyremoved; for example with water, or, if a volatile lcatalystsuch as forexample hydrogen fluoride has been employed, by distillation. Tofacilitate the washing opera tion, the viscosity of the product may bereduced .by adding a diluent or thinningsolvent, such as a fraction ofcracked petroleum. .In general, the 'product is readily miscible withall low-'.

boiling petroleum solvents'containing substantial amounts of unsaturatedand/or aromatic hydrocarbons or derivatives.

The product thus obtained by the preferred process is a drying solu onof solid hydrocarbon resinous material, or a varnish-like material,

which upon application to glass, metals, wood,

iii

gpaint-ingredients to produce'paint compositions I and the like, andupon exposure to the atmosphere yields a hard, tenacious film of goodadhesion. When admixed with a small amount of a drying oil, suchas-linseed oil,-the resulting com-' position forms a good bakinglacquer. It is adapted to admixture with pigments or other of excellentresistance to molds and-like organisms.' By modifying the-process, or byselecting as raw materials liquid phase cracked petroleum, orother'petroleum products which have been subjected to a less drasticpyrolytic treatment carbon materials, varnishes or impregnationcompositions which have exceptional repellent properties for forms ororganic life which attack fibrous organic materials.

Another object of our invention is to prepare by a simplified method,drying solutions of hydrocarbons. a

A' further objectot our invention is to prepare new and useful syntheticresins from inexpensive hydrocarbons. p

Further objects and advantages of this invention will become apparentfrom the following detailed disclosure.

' than the preferred type of raw materiaL-it is possible to preparesolutions of permanently softor tacky products, or even non-drying oilswhich," may, however, be desirable for certain specific applications;for example, some of the wood impregnating and protecting agentsdisclosed In accordance with our invention, a heterogeneouspyrolytically treated hydrocarbon mixture or. fraction thereof,distillablebelow 300 C.

.at atmospheric pressure, is chlorinated substantially to the point ofsaturation, and contacted 5 and claimed, in the co-pending applicationof5 Charley Gustaisson, Serial No. 197,201, flied March 21, 1938. Y

In the resiniflcation reactions oi the prior art,

low melting diiiicultly volatile substances are formed as icy-products.These non-volatile, oily or soft by-products render the reactionproductsnon-drying or tacky, which for the most applications is highlyundesirable. Therefore. in the V production of varnish like materials ithas heretofore been necessary to separate the resinous materials fromthe low-melting, non-volatile byproducts. This has been eiiected bydistilling oil! extraction procedures, or the like.

the low-boiling fractions and subsequently removing'by vacuumdistillation the low-melting, non-drying and/or the resinous materialssubstantially non-volatile at atmospheric pressure. These undesirableby-products may be removed by other processes, such as prolonged steamdistillation, steam distillation at reduced pressure, To prepare avarnish-like materlal, the remaining purified resinous constituents havethen been dissolved in suitable solvents.

In accordance with our invention, the formation of non-drying and/ornon-volatile low- I melting by-products is substantially' avoided. Wehave discovered that it is possible to prepare, from inexpensiveraw-materials, in high yields,

- a drying resin solution 'ora varnish-like mate- The patentsto CL A.Thomas and his co-workers, Nos. 1,836,629; 1,947,626, 1,982,708, and2,062,845, and to C. A. Hochwalt No. 2,035,233, do not contemplate theuse, of chlorine as an aid in securing the desired degree ofpolymerization. The yields of solid resin according to the presentinvention are on the average 400% higher than those obtained by theprocesses disclosed by Thomas and his co-workers .and Hochwalt,

whenapplied to identical raw materials. The

products obtained by our method have a hardness, softening point andadhesion qualities ap-' proximately equal to those of products obtainedby the processes disclosed in the above mentioned patents. erties aresimilar, the chemical properties differ greatly. The resins of thepresent invention contain appreciable amounts of chlorine, generally 3%to 15%, while theresins obtained by the processes disclosed in the above'mentioned patents, are free from chlorine.

The patents to Fulton and Kunc, No. 2,038,558, and to F'rolich, No.2,052,172, employ as raw materials, oils obtained by distillation ofpetroleum tars at 1 pressure-and temperaturesof approximately 150 C.,which corresponds to 'a with the preferred process of the instantinvention, do not produce the drying lacquer-like resin solutionscontemplated by the instant invention, but produce heavy, permanentlysoft or tacky materials of entirely different characteristics. Thetechnical behavior of theFulton and Kunc or Frolich tar'fractions isdifferent from that of the gasoline-like substances used in the practiceof our invention, particu-. larly as applied to-the process ofresiniflcation, and the resins obtained from them are correspondinglydifferent. Therefore, the applicability of a certain type of treatmentto the tar fractions or materials of the prior art does not teach theapplicability of a similar treatment to the chemically entirelydifferent materials co templated by our invention.

The process disclosed by Watermanin Patent No. 2,083,883 is dependentupon a reaction between a chlorinated hydrocarbon material and anon-chlorinated portion thereof, these materials comprising essentiallya, substantial amount of'at least one member of the class consisting ofunsaturated cyclic hydrocarbons and of naphthenes. Incontradi'stinction,v the preferred procedure of our invention consistsof chlorinating the raw material to substantially a saturation point,and adding acondensation catalyst without admixing any non-chlorinatedor partly Although these physical propchlorinated materials.

We have discovered that when the chlorination is carried tosubstantially a' saturation point, the most satisfactory product isobtained. The process of the present invention produces 'a' more highlypolymerized product having a higher melting point than the product ofthe Waterman process, although identical raw materials may be employed.This has been confirmed by numerous experiments When the Watermanprocess is applied to our-preferred type of raw materials, a solutiondrying to apermanently Waterman patent, the resulting product will not idry to a hard, tenacious film on exposure to the boiling range beginningabove 400" C. at atmospheric pressure, or more than one hundredCentigrade degrees above the boiling range of the ,raw materials of theinstant invention. These prior art raw materials .start boillhg at about405 C. at atmospheric .pressuf accom- -panied'by decomposition.Chemicallyfthe tar fractions used as'raw materials by Fulton and Kuncan'd'by Frolich are well known to consist preponderantly of highlycondensed polycyclic substances, while the raw materials employed in thepractice of our invention arepreponderantly i aliphatic or mon -cyclicaromatic or naphthenic substances. stronglybrought out by a comparisonof therechemical nature of the constituents of the ma terials.

The tar fractions, when treated in accordance.

atmosphere, but will remain soft and tacky in contradistinction to theproducts obtained by the present invention. The same is true ifthechlorination is interrupted prior to substantial f saturation, inaccordance with the alternative modification of the process disclosed byWater- .man. 7

For some particular purposes we may advantageously add materialsnot,chlorinated to saturation or non-chlorinated materials prior to the 5polymerization "step. We may also have other resinous materials, orpaint, or lacquer ingredients .present during the polymerization step,or may add diluents or other inert or substantially. inert materials toobtain a more advantageous viscosity for the operations, or otherwisemore favorable operating conditions or results.- A good baking lacqueris obtained by having present linseed oil during the polymerizationstep..

, However, such additions, while sometimes advantageous-or desirable, donot form any essential part of-our, invention, and the invention j doesnot contemplate the addition'of any non- 2,261,748 I chlorinated orpartly chlorinated material consisting essentially of a substantialamount of at least one member of the class consisting. bfunsaturatedhydrocarbons and of naphthenes prior to the polymerizationstep, asdisclosed 'by Waterman.

, The patent to C. C. TownepNo. 2,084,927., contemplates the preparationof resins by condensing benzol with halides of normally gaseousolefines. The preferred raw materials of our inchlorination, and a thickor heavy. substantially non-drying product of-high chlorine content is iproduced which is satisfactory, for example, as

vention do not contain any halides of normal- Y ly gaseous olefines, norare any such halides formed during the chlorination step of theprocess.This inventionis thus clearly distinguished from theTowne disclosure.

Various aspects of our invention are illustrated in the followingexamples. As is apparent from the foregoing, the invention'is capableof) great variation, and is not limited to vthe particular rawmaterials, procedures and manipulative'steps set forth in the examples'Example 1 l 100 parts by weight of a fraction of a petroleum productprepared by catalytic condensation at 1l50 C. to 1200 C. of gases formedby vapor phase cracking of petroleum, said fraction boiling between 40and 200 C. at atmospheric pressure and having a specific gravity of0.840 and a bromine number of 0.474 is chlorinated as long asthematerial, avidly absorbs chlorine: During 1 the chlorination it isnecessary that the matemay be advantageously. employed and even lowerrial be cooled, and the temperature is maintained Y between 20 and 60C., preferably between and C- The chlorination is discontinuedwhen thetemperature begins to decrease spontaneously, indicating that thoseconstituents which readily absorb chlorine have becomesubstantially'saturated. The specific gravity of thechlorinated'material is of the order of about 1.1.

. rine content.

a wood impregnant.

To the chlorinated product is gradually intermixed, under agitation, 4%dry, finely divided When greater proportions aluminum chloride. ofaluminum chloride are employed, the resulting product will have a lowerchlorine content. For example-if 18% aluminum chloride is employed, thechlorine content of the solid resin .constituent of the end product willbe of the order of 7%, while .in the present example, the chlorinecontent of the/resin is about 13%. lower proportions of the catalystareemployed,

the resulting product will have a lower melting point and may be'soft oreven non-drying in character at ordinary temperatures. These solutionsof low melting point resins obtained by polymerization with less than 4%aluminum chloride, orwith condensation talysts of lesser emcacy, such asferric chloride, tannic chloride,

zinc chloride, and the like, are particularly emcient as .vermlnresistant or repellent coating materials, possibly because'of their highchlo- From the foregoing, amount of catalyst may be varied according tothe properties which are desired in the final product. From 21% to 18%aluminum chloride or higher proportions to suit particular requirements,but usually we prefer to employ about 4% to 6% aluminum chloride, orequivalent proportions of other catalysts of similar action. Boronfluoridelis a satisfactory catalyst for the pur poses of ourinvention,the former tending to produce more brittle resins, and if employed inThe bromine number of the chlorinated mate rial has been decreased toapproximately 0.004. indicating that the material is a substantiallysaturated composition.

In this example, the chlorination is carried out by induction of gaseouschlorine, in darkness, in

the absence of water and chlorination catalysts. No appreciabledifference in the end product was observed, however, when thechlorination was carried out in light or in darkness, in the presence ofor in the absence of water, or of a susan aqueous solution of calciumhypochlorite, or

methods known to theart. When the chlorinapension of calcium carbonatein water or with with liquid chlorine, or by other chlorination tion wascarried out under anhydrous conditions,

- the'resulting product was at first darker in color than when water waspresent, but the product became lighter in color on continuation of thechlorination, so that the difierence in the color of the end product wasnot appreciable. These experiences with different methods ofchlorination indicatethat wide variations in the procedure ofchlorination may be employed without greatly'aifecting the yield orresultspf the proo ess, or the character of the product.

However, when the chlorination was carried out in the presence of avcatalyst tending to promote the introduction of. chlorine into the.arc-.- matic nuclei, a group of catalysts which is well defined antienumerated in the adv'anced textbooks on preparative organic chemistry,the most commo used catalyst 'of this class being alucondensation willoccur simultaneously with the minum' c oridefiron, and iron ,plusiodine, a

excess, totally insoluble black products.

During the addition'of the catalyst, the temperature of the mass rises,and we therefore, prefer to add the catalyst gradually, in smallportions, so that'the temperature does not rise too rapidly, andpreferably is maintained at .about 50C. If the reaction mixture'iscooled too vigorously during this stage. of the process,

the reaction product will not have'the property of drying .to form .ahard film, and the resinous product when isolated is much softer thanwhen the product is prepared by allowing the'reaction to proceed at thepreferred temperature. However, there are instances where a' softerproduct may be desired, and the reaction may then be carried out atlower temperatures, even as lowas 0 C. or lower. Rea otl above thepreferred range of from about 40 to 50 C. often result in the productionof products which are darker in color, and somewhat lower maintained ata temperature of about C. until cessation of the'evolutio'n of hydrogenchloride gas, which began onthe addition of the catalyst. Usually theevolution of hydrogen chloit is apparent that the I on at temperatures.t

chloride may be recovered and the chlorine separated and -employed inthe chlorination of further quantities of the raw material. The reactionor polymerized productwas cooled or allowed 'the product by the.addition of a suitable diluent or solvent. Particularly suitable forthis purpose arehydrocarbon fractions containing unsaturated bythe factthat no temperature change was ob.-

served, and no hydrogen chloride was evolved. Similar end products ofthe process were obtained when no added diluent or solvent was added beUnless there isa sufilcient difference in the gravities, separation isdiflcult. The solution thus obtained was repeatedly washed withwater,thenmixed with calcium chloride or some other suitable dehydrating agentto remove the water, and the dehydrating agent then removed by-filtration, decantation, or by centrifugal action. The yield was about135 parts by weight of adark brown resin solution containingapproximately 60 parts by-weight of a'hard solid resin. This resinsolution, when applied to a surface, hardened within 4 hours to form ahard, tenacious-film of good adhesion to glass, concrete. .metals, andlike surfaces, and was resistant to water, acids and alkalies. Uponadmixture of pigments such ..as lithopone, iron oxide, aluminum powder,and the like, the drying time ofthe resin solution is greatly reduced,as disclosed and claimed in the Serial No. 197,201. filed March 21,1930.

-E'zample 2 '100 parts by weight of a motion or a polycondensate,prepared by catalytic condensation at 1150 to 1200 F. of the gaseousby-products from the operation of cracking gasoil in liquid phase underhigh pressure, boiling between and 200 C. at atmospheric pressure and.having a specific gravity of 0.784 and a bromine number of 0.924 werechlorinated as in Example 1. Six parts by weight of aluminum-chloridewere added, while agitating the mass. When the initial reac; tionsubsided, the mixture was heated with steam at substantially atmospheric1 /2 hours. The resulting material was diluted with parts by weight ofethyl acetate, washed with water, dried with calcium chlorida andcentrifuged to remove these agents. The yield was 113 parts by weightof'a dark brown liquid con- 2,ae1,74s 'ride persists about minutes.Thehydrogen taining about 43% solid as. This liquid, when exposed to theatmosphere in thin layers, dried to form a hard tenacious film of goodadhesion to glass, metals, wood, and like surfaces. 1

Emmplc 3 v parts by weightof a hydrocarbon polycondensate prepared bycatalytic condensation at 1050 to 1100 F. of the gaseous by-productsfrom vapor phase cracking of petroleum were chlorinated, substantiallyto saturatiom-by induction of gaseous chlorine at a temperature between40' and 50 C. This polycond raw material had a boiling range between 40and C. at

and/or aromatic constituents. In this particular 15 atmspheflc Pressure.Specific m 1' example. we employed 35-parts by weight of the l bmmmenumber of 1.308- P mmple; non-chlorinated fraction used as the raw mate-3 01 the chlorination, 12 parts by weight 0 m orthe examph This materialwas here aluminum chloride were added gradually'while added merely as adiluent or solvent. No reacagitating the mass- The ensuingPolymerlllflllll tion occurred on the addition thereof as evidenced 20reactmn bmught t0 mpleuon 7 1"" for about ,6 hour with steamatsubstantially atmospheric pressure. (SO-parts of benzol were added asa diluent. The composition was washed with watendried with calciumchloride, and" centrifuged-to remove the drying agent. The yieldacetate, and the like. It is compatible with linseed oil, partly solublein saturated hydrocarbons, and insoluble in water, lower aliphaticalwhich it is desired to remo fore, washing the product with water, orwhen 25 other solvents, such as carbon tetrachloride or parts by t? drem ethyl acetate were employed, and the sole purwmch' when 9 ed "7pose-and function of the addition ofrthese subs the like surlflacei andto e atmosp 9" stanceswas to facilitate washing by reducing the quid"dgned mm tenacious.

the viscosity. '30 9m v It is preferable to add "such amountsof the 4solvent or diluent'so that the specific gravity bans of the resultingresin solution is different from igg fl gfig zfggj g fi faf 2 mg: thatof the liquid used washing the catalyst at atmospheric pressure untilthe volatile conto facilitate the separation-of the different layers. 35

Peculiarly, to ,obtain the greatest P s ble deco! orization of theresin, it is essentiai to remove the very last traces ofvolatileconstituents prolonged heating in a vacuum prior totheexpurities greatly enhance the solubility in extraction solvents ofthose dark colored constituents which it is desired to remove.

with Examples 2 and 3 also,v on removal of the volatile constituents,produce solid resins of properties similar to thoseof the resinsdescribed in this example.

" reun on s 300 parts by weight of a fraction of vapor phase crackedpetroleum, boiling between 30' and 220 C. at atmospheric pressure andhaving a bromine number of 0.515 and a specific gravity 65 of 0.868,were chlorinated in the absence of water'by induction of gaseouschlorine. The temperature during the chlorination was maintained between40 to 50 C. After about '70 minutes, the temperature began to decline,and the chicpressurqfor about 7 line began to pass through the solutionunabsorbed. The yield was 420m of a light brown, clear liquid, having aspecific gravity of- 1.103.

To 100 parts by weight of this chlorinated prodaluminum chloridegand thepolymerizationwas traction step. Even slight traces of these im-- Theresin solutions prepared in accordance.

uct was added 1 part by weight of vanhydrous A 2,261,748 allowed toproceed for 90 minutes at a temperature of 100", C. The resultingproduct, without dilution, was washed with water and dried with calciumchloride. The yield was'80 parts byweight of a dark brown-oily liquid,which when applied to a surface in a thin layer and exposed employed.With 4% catalyst instead of the 1% used in this example, the resinsolution obtained will dry readilyto a hard, tenacious film. The

sdft product obtained in this example has a higher chlorine content, andis saitisfactoryfor use as a vermin repellent, as a moldicide in paints,or as a plasticizer.

Example 6 300Jparts'by weight of a petroleum product prepared bycatalytic condensation at .1150 to 12001 F. of gases formed by vaporphase cracking of petroleum, said fraction boiling between 40 and 200 C.at atmospheric pressure and having a bromine number of 0.474 and aspecific gravity-of 0.840, was chlorinated by induction of gaseouschlorine at to C. substantially to saturation in the'presence of 40parts by .weight of iron powder. Under these conditions,

naturally some ferric chloride was formed and was present duringchlorination. The latter part of the simultaneous chlorination andpolymerization was carried outat a temperature of about C. The productwaswashed with water to remove the catalyst, dried with calciumchloride,

and centrifuged. The yield was 380 parts of a dark brown, viscousliquid, of faint odor, and

Example 7 parts by weight of-a raw distillate ob- 'tained from highpressure liquid phase cracking of gas oil, boiling entirely below 300 C.at atmospheric pressure, and having a specific gravity of. 0.735 and abromine number .of 01492,

were chlorinated'as described in Example 1, the

temperatureduring the chlorination being maintained between 20 and 50 C.The yield of chic.- 1

rinated product was 162 cr wl of a liquid having a specific gravity of1.136 Further processing carried out as described in Example 1 produced.

133 parts of alacquen-like liquidIwhich liowever,

dried moreslowly than the product 01 Example 1,

andon removal of the volatile constituents forms asofterresin.

Exampleil p 100 parts byweight of a fraction of a liquid obtained bypolymerization of ethylene, with phosphoric acid as a catalyst at 60atmospheres pressure and 280 C., this fraction boiling be- F fi 'actionboiling, above 400C. at atmospheric.

tween 40 and 300 C., and having a bromine number of 0.540, weresubjected to the treatment described in detail in Example 1. The yieldwas parts-of a lacquer-like liquid, which on exposure to. the atmospherein a thin layer dried rapidly to form ahard, tenacious film of excellentadhesion to wood, glass, steel, and the like. Further tests were carriedout 'with' narrower n fractions ofthe raw materials mentioned above.

These tests -included experiments with fractions of each ofthehydrocarbon products described in the above examples, these fractionsboiling between 20 and 50 C., 50 and 60C., 60 and 74 C., 92 and 128 C.,and 160 C.,

and C., 160 and 183 C., 140 and 260 C.,

and 210 C., 210 and.240 C., and 240 and 300 C., and 280 and 300 C., atatmospheric 2 pressure. The results of this experimental work 10 provedthat the process disclosed herein operates over this entire range of rawmaterials, and that the results are not greatly dependent upon the' low,the product may be a non-drying oil, useful, for example, as a verminrepellent That these widely different fractions of raw materials aresatisfactory for the purposes of this invention illustrates that thereaction is of very general applicability, and that it is not dependenton any particular chemical entity or entities. The

wide variation in chemical structure between the 1 substances containedin the various fractions having different boiling ranges, iswell knownin the art, and is particularly. apparent from the recent tabulations ofproducts isolated from hydrocarbon fractions, for example, see PhysicalConstants of Principal Hydrocarbons by M. P. Doss; NewYork, 1939.However; from a practical comhnercial standpoint, we prefer to usefractions of a wide boiling range such as raw materials, a substantialpart of which boils in the range of from 80 to 240 C. at atmosphericpressure and having a bromine number exceeding 0.400, or such rawmaterials which have a boiling range of from 20 to 300 C., and having a.bromine number exceeding 0.314.

Petroleum products boiling higher than 400 C, show an entirely differentbehavior when an attempt is made to subject them to the method of theinstant invention. Such high boiling petroleum tar fractions arecomposed principally of very highly condensed aromatic substances,

ployed in the practice. of our invention, which are Y 1 of aliphatic, orof monocyclic aromatic or naphthenic substances. The chemicalcharacter,-

istics and behaviors of these two classes of a raw -materials areobviously greatly diiferent. If a tar pressure, such as the materialscontemplatedby Fulton and Kunc or by Frolich'in Patentsv No.

preferred practice of our invention, as disclosed tle utility asvcompared to the product obtained chemically different, as is apparentand obvious from'the highly polycyclic character of the raw materials.gProductsjobtained' by treatment in by Fulton and Kline and by Erolich,as well as to the products of theinstant application. While the additionor use of-any chemicals not Generally, fractions boiling ucts alsodecreases,- and if the boiling rangeis I in contra-distinction to theraw materials emr 2,038,558 and N0.- 2,052,'172,-is subjected to the.

by the use of our raw materials. The character. oftheresinsobtained fromthe tar fractions is accordance T with our invention of crackedpetroleum fractions boiling between 300 and 400 C.,-show some similarityto the resins disclosed previously discussed is unnecessary andnon-essential to the success of the process, it is apparent and obviousthat the addition of various substances at the different stages of theprocess maymodify the ultimate product, and that at times suchmodifications may be desirable. Therefore, the present invention is notlimited to the exact procedure of the examples, and the spirit and scopeof our invention are not avoided by merely adding some inert material,.or some material performing an obvious function prior to thechlorination step, or at anyother stage of the process. It is fullyapparent that for some purposes it may be convenient or desirable to addpigments, or fillers at some intermediate stage in the process, or toadd some other lacquer or paint ingredients, or even to co-polymerizethe product a with some drying oils, or non-drying oils or fatderivatives, chlorinated or otherwise, for example to further enhancethe water resistance of the product. All of these and like modificationsare considered within the spirit and scope of this invention.

Our invention does not contemplate, however,

and hydrogen on pyrolysis, and ethylene polymerized to yield fractionsof satisfactory properties. g

The raw material is not limited to products of petroleum origin, sincesimilar products are-obtainable, for example, by variousprocessesinvolving hydrogenation of coal, and concurrent or subsequentpyrolytic treatment of the substances thus obtained.

Since it appears that there is no suitable generic term embracing thevarious substances which are satisfactory as raw materials for thepurposesof our invention, and the obvious equivalents of suchmaterials,- we refer 'to these substances. as pyrogenic hydrocarbonmaterials meaning thereby a mixed hydrocarbon material resulting from atreatment sufficient tocause an appreciable degree of thoserearrangements or reactions which are known in the art as typical ofpyrogenic reactions and which might be attributed to interaction of freeradicals. These materials contain an appreciable amount i i-unsaturatedaliphatic The addition of such materials would cause a fundamentaldeviation in the resinification reaction, and would cause the formationof products disclosed by Waterman in Patent No. 2,083,883, which aredistinct and entirely different from the resins and resinous materialscontemplated by our invention;

The influence of various variables on the process and product isdiscussed in considerable detail in the description of Example 1. Thesecomments are generally applicable.

With respect to the raw materials, the process is not limited toproducts obtained by any particular process. Apparently, fractionsboiling below 300 C. atatmospheric pressure are representative materialswhichhave been subjected to' a pyrolytic treatment suficient to inducechanges or rearrangements in the molecules which might These materialsare mixtures of various chemical entities, always containing a fairpercentage of unsaturated aliphatic or aromatic substances or ofnaphthenes. The bromine number of the or aromatic or naphthenichydrocarbons," as evidenced by a bromine number of at least 0.090.usually considerably higher. As typical examples 'of'these materialswhich we term-pyrogenic hydrocarbon materials may -be mentioned theproducts'resulting from all cracking treatments, including catalyticcracking procedures, such as the Houdry processes, from" catalytic ornoncatalytic high temperature polymerization of hydrocarbon gases,regardless of the origin of; such gases and of the particulartemperatures,-'pres-" sures and catalysts employed, catalyticallydehydrogenated hydrocarbon products, and products ;ha'ving a compositionsubstantially similar to that. of such substances, such similarity beingexpressed in anapproxirhately similar (say within about 10%) boilingrange, ratio between saturated and unsaturated,-naphthenic and aromaticconstituents, and consequent similar behaviors when subjected to the, rinification treatments of this invention,

be attributed to interaction of free radicals;

From the foregoing disclosure, it is apparent that the invention is'capable of wide variations and modifications within wide limitsdepending upon the particular applications contemplated, and upon theproperties desired in the final end product.- The foregoing examples arenot to be construed in any sense of limitation, but are,

. given merely to illustrate the invention, which is to be limited onlyby the claims which follow, in

preferred raw materials exceeds 0.400, although a softer-resin of fairproperties was obtained from a fraction of liquid phase cracked gasolinehaving a bromine number of only 0.314, and although a usefulimpregnation compound was prepared from a fraction having a brominenumber of as low as 0.090.

' such as liquid'or vapor phase cracking gases, or natural gas, or asingle chemical entity such as ethylene oracetylene. Even methane couldbe products, hydrocarbons obtained by polymeriza-' 1 tion of crackinggases, hydrocarbons obtained by used as the initial materialforproducing fractionssuitable for thepurposes of our invention sincemethane -is well known to form ethylene which it is intended to claimall novelty inherent in this invention as broadly as possible in view ofthe prior art.

We claim; v 1. A composition of matter-comprising the product of .theprocess consisting essentially ofchlorinating substantially tosaturation, substantially unsaturated hydrocarbon material selected fromthe group consisting of cracked petroleum polymerization of naturalgases and hydrocarbons obtained by hydrogenation of coal," said hydro--carbon material having a boiling range below 3 C; at atmosphericpressure and polymerizing t e chlorinated material by the use of aFriedelv Crafts type catalyst.

2. A composition of matter comprising the product of the processconsisting essentially of chlorinating hydrocarbon materialsubstantially to saturation, said hydrocarbon material being selectedfrom the group consisting of cracked petroleum products. hydrocarbonsobtained by polymerization of cracking gases, hydrocarbons obtained bypolymerization of natural gases and hydrocarbons obtained byhydrogenation of coal, said hydrocarbon material having a bromine numberexceeding .314 and being distillable below 300 C. at atmospheric"pressure, polymerizing the chlorinated material by the use of aFriedel-Crafts type catalyst, removingthe catalyst and removing thevolatile constituents.

3. A composition of matter comprising the chlorinating, substantially tosaturation, a disproduct of the process consisting essentiallyof Vtillate of a cracked petroleum pHJ'duct, said distillate beingsubstantiallyunsaturated and hav ing a boiling range below 300 C. atatmospheric 4. A composition of matter-comprising the product of theprocess consisting essentially of chlorinating. hydrocarbon materialobtained by polymerization of cracking gas constituents, subpressure,and polymerizing the chlorinated ma- .terial by the use of aFriedel-Crafts type catalyst.

stantially to saturation, said hydrocarbon mate- I rial beingsubstantially unsaturated and having a boiling range below 300 C. atatmospheric pressure, and polymerizing the chlorinated material I by theuse of a Friedel-Crafts type'catalyst.

5. A composition of matter comprising the.

product of the process consisting essentially of chlorinatinghydrocarbon materially obtained by polymerization of natural gases,substantially to saturation, said hydrocarbon material having a brominenumber exceeding .314, and a boiling range below 300 C. at atmosphericpressure, and polymerizing the chlorinated material by the use of aFriedel-Crafts type catalyst.

6. A composition of matter comprising the product of the process whichessentially consists of chlorinating, substantially to saturation,hydrocarbon material containing a substantial proportion of unsaturatedhydrocarbons, said material being selected from the group consisting ofI cracked petroleum products, hydrocarbons obtained by polymerization ofcracking gases, hy-

drocarbons obtained by polymerization of natural gases, and hydrocarbonsobtained by hydrogenasubstantial proportion of unsaturated hydrocarbons,said material being selected from the groups consisting of crackedpetroleum products hydrocarbons obtained by polymerization of crackinggases, hydrocarbons obtained by polymerization of natural gases, andhydrocarbons obtained by hydrogenation of coal, said hydrocarbonmaterial having a boiling range below 300 C. at atmospheric pressure;and simultaneously poymerizing the chlorinated material.

8. A composition of matter comprising the product of the processconsisting essentially of chlorinating hydrocarbon materialsubstantially to saturation, said hydrocarbon material being selectedfrom the group consisting of cracked petroieum products, hydrocarbonsobtained by poly- -merization of cracking gases, hydrocarbons obtainedby polymerization of natural gases, and hydrocarbons obtained byhydrogenation of coal,

said hydrocarbon material having a bromine.

number exceeding .314 and being distillable below 300 C. at atmosphericpressure and polymerizing the chlorinated material by the use ofaluminum chloride.

9. A lacquer-like resin solution obtained by the process which consistsessentially of chlorinating,

- substantially to saturatio'rr'hydrocarbon material containing asubstantial proportion of unsatuof chlorinating, subst ntially tosaturation, a vation of coal, said hydrocarbon material havinga Iboiling range below 300C. at atmospheric prestemperature between 20 and60 C.; and polymerizing the chlorinated material by the use of aFriedel-Crafts type catalyst at a temperature between 20 and 60 C. d

7. A composition of matter comprising the product of the processessentially consisting of chlorinating in the presence of a catalysttending to promote the introduction of chlorine in arosure: thechlorination being carried out at a matic nuclei, hydrocarbon materialcontaining a por phase cracked hydrocarbon of petroleum origin,distillable below 300 C. at atmospheric pres-.-

sure and having a bromine number exceeding .314,

and polymerizing the chlorinated material by the use of a Friedel-Craftstype catalyst.v

11. A composition of matter comprising the product of the process ofchlorinating, substantially to saturation, a vapor phase crackedhydrocarbon material of petroleum origin, distillable below 300 C. atatmospheric pressure, and polymerizing the chlorinated material by theuse of a Friedel-Crafts type catalyst without the addition ofnon-chlorinated or partly chlorinated ma- Y terials prior to thepolymerization step. R. WALLER; CHARLEY GUSTAFSSON.

